Cobalt‐Driven Cross‐Dehydrocoupling of Silanes and Amines for Silylamine Synthesis

Abstract Cobalt complexes featuring triazine‐based PNP ligands have proven to be exceptionally active and chemoselective pre‐catalysts in facilitating the dehydrogenative coupling between silanes and amines, leading to the synthesis of diverse aminosilanes. Notably, even challenging substrates exhibited high reactivity. The catalyst‘s unique feature of avoiding coupling with tertiary silanes enhances process chemoselectivity. It facilitates a more precise synthesis of silylamines possessing of SiH 2 −N and SiH−N motifs, overcoming challenges associated with broader reactivity seen in previous systems. In terms of its remarkable chemoselectivity, it is also noteworthy that the catalytic system exhibits both versatility and efficacy in converting substrates with untouched double and triple carbon‐carbon bonds. This accomplishment is particularly significant, given previous challenges brought about by the activity of commonly employed catalysts in the competitive hydrosilylation process.